EP0022971A1 - Procédé pour la préparation de dérivés de l'acide 3-(2,2-dichlorovinyl)-2,2-diméthyl-cyclopropane-1-carboxylique - Google Patents

Procédé pour la préparation de dérivés de l'acide 3-(2,2-dichlorovinyl)-2,2-diméthyl-cyclopropane-1-carboxylique Download PDF

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Publication number
EP0022971A1
EP0022971A1 EP80103847A EP80103847A EP0022971A1 EP 0022971 A1 EP0022971 A1 EP 0022971A1 EP 80103847 A EP80103847 A EP 80103847A EP 80103847 A EP80103847 A EP 80103847A EP 0022971 A1 EP0022971 A1 EP 0022971A1
Authority
EP
European Patent Office
Prior art keywords
dimethyl
cyclopropane
carboxylic acid
formula
acid derivatives
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP80103847A
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German (de)
English (en)
Other versions
EP0022971B1 (fr
Inventor
Hellmut Dr. Hoffmann
Fritz Dr. Maurer
Uwe Dr. Priesnitz
Hans-Jochem Dr. Riebel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19792929725 external-priority patent/DE2929725A1/de
Priority claimed from DE19803009242 external-priority patent/DE3009242A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0022971A1 publication Critical patent/EP0022971A1/fr
Application granted granted Critical
Publication of EP0022971B1 publication Critical patent/EP0022971B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • the invention relates to a new process for the preparation of known 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropane-1-carboxylic acid derivatives.
  • Examples include 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid, its sodium and potassium salt and 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid methyl ester, ethyl ester, -n- propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, sec-butyl ester and tert-butyl ester.
  • Examples include dichloromethane-phosphonic acid dimethyl ester, diethyl ester and diphenyl ester.
  • the compounds of the formula (III) are known or can be prepared by processes known per se (cf. Synthesis 1975, 535-536; Tetrahedron Letters 1975, 609-610; ibid. 1975, 4409-4410).
  • Dichloromethane-phosphonic acid ester of the formula (III) is obtained, for example, by reacting dichloromethanephosphonic dichloride (cf. GB-PS 707 961) with sodium or potassium salts of hydroxy compounds, such as e.g. with sodium or potassium methylate, ethylate, -n- and -isopropylate, -n-, iso-, sec- and tert-butoxide, optionally in the presence of a diluent, e.g. Toluene, at temperatures between 0 and 50 ° C. To clean the products, distillation is optionally carried out after filtration.
  • a diluent e.g. Toluene
  • the process according to the invention is preferably carried out using diluents.
  • diluents Practically all inert organic solvents, in particular aprotic polar solvents, are suitable as such.
  • ethers such as Gylcol dimethyl ether, Diglycol dimethyl ether, tetrahydrofuran and dioxane, carboxamides such as Dimethylformamide, Dimethylacetamide and N-methyl-pyrrolidone, sulfoxides and sulfones such as dimethyl sulfoxide and tetramethylene sulfone, phosphoric acid amides such as hexamethyl phosphoric acid triamide, and nitriles such as acetonitrile and propionitrile.
  • ethers such as Gylcol dimethyl ether, Diglycol dimethyl ether, tetrahydrofuran and dioxane
  • carboxamides such as Dimethylformamide, Dimethylacetamide and N-methyl-pyr
  • the bases customary in organic chemical synthesis can be used.
  • these include in particular alkali hydroxides, e.g. Sodium and potassium hydroxide, alkali alcoholates, e.g. Sodium and potassium methylate, sodium and potassium ethylate, sodium and potassium isopropylate, sodium and potassium tert-butoxide, alkali metal hydrides, e.g. Sodium and potassium hydride, alkali amides, e.g. Sodium and potassium amide, alkyl lithium compounds such as e.g. Butyllithium, as well as amines, e.g. Diazabicyclonones and diazabicycloundecene.
  • alkali hydroxides e.g. Sodium and potassium hydroxide
  • alkali alcoholates e.g. Sodium and potassium methylate, sodium and potassium ethylate, sodium and potassium isopropylate
  • sodium and potassium tert-butoxide alkali metal hydrides,
  • Alcoholates are particularly preferred as bases.
  • the reaction temperature is kept between -50 and + 50 ° C, preferably between -30 and +3 0 ° C.
  • the process according to the invention is generally carried out at normal pressure.
  • the starting materials of the formulas (II) and (III) are initially introduced in one of the diluents specified above at temperatures between -30 and + 10 ° C. and a solution of a base in one of the diluents specified above is added dropwise . Then the reaction mixture is allowed to come to room temperature and stirred for a few hours.
  • the reaction mixture is poured into water and extracted with a water-immiscible solvent, such as e.g. Methylene chloride.
  • a water-immiscible solvent such as e.g. Methylene chloride.
  • the extracts are washed with dilute sodium hydroxide solution and then with water, dried and filtered.
  • the solvent is drawn off from the filtrate and the product remaining as residue is purified by vacuum distillation. The boiling point is used for characterization.
  • the process according to the invention relates to the stereoselective preparation of compounds of the formula (I) which are obtained either in the form of the individual stereoisomers or as mixtures of stereoisomers.
  • the 2,2-dimethyl-3- (2,2-dichloro-vinyl) -cyclopropane-1-carboxylic acid derivatives to be produced by the process according to the invention can be used as intermediates for the preparation of pyrethroids which have an insecticidal and acaricidal action (cf. DE-OS 2 326 077).
  • reaction mixture is poured into 400 ml of water.
  • aqueous solution is extracted twice with 200 ml of methylene chloride.
  • the combined organic extracts are washed once with 100 ml of 5% sodium hydroxide solution and twice with water, dried over sodium sulfate and then evaporated.
  • the backlog will. fractionally distilled. 42 g (88.6% of theory) of ethyl 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropane-1-carboxylate are obtained in the form of a colorless oil with a boiling point of 80-95 ° C./ 2 mbar.
  • a solution of 15 g of sodium ethylate in 50 ml of dimethylformamide is stirred with a solution of 24 g (0.1 mol) of 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid and 22 g ( 0.1 mol) of diethyl dichloromethane-phosphate in 100 ml of tetrahydrofuran added dropwise.
  • the reaction mixture is stirred for 15 hours at room temperature (15 to 25 ° C), concentrated under reduced pressure and dissolved in 200 ml of water.
  • the aqueous solution is shaken with diethyl ether, clarified with activated carbon, acidified with hydrochloric acid after filtration and then shaken with methylene chloride.
  • Dichloromethane-phosphonic acid esters of the formula (III) to be used as starting materials can be prepared, for example, as follows: 266 g (2 mol) of aluminum chloride are added in portions to a mixture of 720 g (6 mol) of chloroform and 274 g (2 mol) of phosphorus trichloride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP80103847A 1979-07-21 1980-07-07 Procédé pour la préparation de dérivés de l'acide 3-(2,2-dichlorovinyl)-2,2-diméthyl-cyclopropane-1-carboxylique Expired EP0022971B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2929725 1979-07-21
DE19792929725 DE2929725A1 (de) 1979-07-21 1979-07-21 Verfahren zur herstellung von 3-(2,2-dichlor-vinyl)-2,2-dimethylcyclopropan-1-carbonsaeureestern
DE19803009242 DE3009242A1 (de) 1980-03-11 1980-03-11 Verfahren zur herstellung von 3-(2,2-dichlor-vinyl)-2,2-dimethyl-cyclopropan-1-carbonsaeure-derivaten4
DE3009242 1980-03-11

Publications (2)

Publication Number Publication Date
EP0022971A1 true EP0022971A1 (fr) 1981-01-28
EP0022971B1 EP0022971B1 (fr) 1983-03-16

Family

ID=25780139

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80103847A Expired EP0022971B1 (fr) 1979-07-21 1980-07-07 Procédé pour la préparation de dérivés de l'acide 3-(2,2-dichlorovinyl)-2,2-diméthyl-cyclopropane-1-carboxylique

Country Status (8)

Country Link
US (1) US4296241A (fr)
EP (1) EP0022971B1 (fr)
BR (1) BR8004486A (fr)
DD (1) DD152125A5 (fr)
DE (1) DE3062343D1 (fr)
DK (1) DK309080A (fr)
HU (1) HU182691B (fr)
IL (1) IL60630A0 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USH49H (en) 1983-01-10 1986-04-01 Fmc Corporation Process for producing 3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylates
US6464341B1 (en) 2002-02-08 2002-10-15 Eastman Kodak Company Dual action thermal actuator and method of operating thereof
JP4765353B2 (ja) * 2004-03-22 2011-09-07 住友化学株式会社 （１−アルケニル）シクロプロパン化合物の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1807091A1 (de) * 1967-11-10 1969-10-02 Roussel Uclaf Direction Des Br Verfahren zur Herstellung einer Cyclopropan-carbonsaeure und die dabei erhaltenen Produkte
DE1935386A1 (de) * 1968-07-12 1970-01-15 Roussel Uclaf Verfahren zur Herstellung von Cyclopropanderivaten und die dabei erhaltenen Produkte
EP0000345A1 (fr) * 1977-07-06 1979-01-24 Bayer Ag Dérivés phénoxybenzyloxycarbonyles substitués, leur procédé de préparation et leur utilisation comme insecticides et acaricides
EP0006205A1 (fr) * 1978-06-21 1980-01-09 Bayer Ag Procédé pour la préparation de dérivés d'acides chlorostyrène cyclopropane carboxyliques

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3849474A (en) * 1972-03-27 1974-11-19 Ayerst Mckenna & Harrison 11-deoxyprostaglandin derivatives and process therefor
US4024163A (en) * 1972-05-25 1977-05-17 National Research Development Corporation Insecticides
GB1446304A (en) * 1972-05-25 1976-08-18 Nat Res Dev 3-substituted cyclopropane carboxylic acids and derivatives thereof
EP0007142B1 (fr) * 1978-07-19 1982-05-12 Shell Internationale Researchmaatschappij B.V. Produits intermédiaires de la préparation d'esters cyclopropanecarboxyliques et procédé pour leur préparation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1807091A1 (de) * 1967-11-10 1969-10-02 Roussel Uclaf Direction Des Br Verfahren zur Herstellung einer Cyclopropan-carbonsaeure und die dabei erhaltenen Produkte
DE1935386A1 (de) * 1968-07-12 1970-01-15 Roussel Uclaf Verfahren zur Herstellung von Cyclopropanderivaten und die dabei erhaltenen Produkte
EP0000345A1 (fr) * 1977-07-06 1979-01-24 Bayer Ag Dérivés phénoxybenzyloxycarbonyles substitués, leur procédé de préparation et leur utilisation comme insecticides et acaricides
EP0006205A1 (fr) * 1978-06-21 1980-01-09 Bayer Ag Procédé pour la préparation de dérivés d'acides chlorostyrène cyclopropane carboxyliques

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 92, Nr. 17, 28. April 1980, Zusammenfassung Nr. 146332f, Columbus, Ohio, (US); & JP-B-54 032 772 (SUMITOMO CHEMICAL CO. LTD.) (16-10-1979) *
CHIMIA, Band 28, Nr. 11, November 1974, Zurich, (CH) H. ZIMMER et al: "Syntheses with alfa- heterosubstituted phosphonate carbanions (III): diacetylenes and substituted vinyl chlorides", Seite 656 *
SYNTHESIS, Nr. 8, August 1975, P. SAVIGNAC et al: "Alpha-Chlorination and carbonyl olefination", Seite 535 *

Also Published As

Publication number Publication date
HU182691B (en) 1984-02-28
US4296241A (en) 1981-10-20
DK309080A (da) 1981-01-22
EP0022971B1 (fr) 1983-03-16
BR8004486A (pt) 1981-01-27
DE3062343D1 (en) 1983-04-21
IL60630A0 (en) 1980-09-16
DD152125A5 (de) 1981-11-18

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